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Mechanism of the Dehydrogenative Silylation of Alcohols Catalyzed by Cationic Gold Complexes: An Experimental and Theoretical Study
Author(s) -
Labouille Stéphanie,
EscalleLewis Aurélie,
Jean Yves,
Mézailles Nicolas,
Le Floch Pascal
Publication year - 2011
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201002150
Subject(s) - cationic polymerization , xantphos , silylation , catalysis , counterion , hydride , chemistry , catalytic cycle , medicinal chemistry , combinatorial chemistry , ion , polymer chemistry , organic chemistry , hydrogen , palladium
The catalytic activity both of cationic [(XDPP)Au][X] (XDPP=bis‐2,5‐diphenylphosphole xantphos X=BF 4 ) and of the isolated gold hydride complex [(XDPP) 2 Au 2 H][OTf] in the dehydrogenative silylation process is presented. A parallel theoretical study using density functional theory revealed a mechanism involving the counter anion as a co‐catalyst, which was experimentally confirmed by testing various counterions (X=OTf, NTf 2 , PF 6 ). Finally, a “Au 2 H + ” species was determined as the intermediate during the catalytic cycle, which correlates well with the experimental findings on the first example of catalytic activity of an isolated “AuH” complex.